Ding Jianfu, Li Zhao, Kodra Oltion, Couillard Martin, Ouyang Jianying, Lapointe François, Malenfant Patrick R L
Security and Disruptive Technologies Research Centre, National Research Council of Canada, 1200 Montreal Road, M-12, Ottawa, Ontario K1A 0R6, Canada.
Energy, Mining and Environment Research Centre, National Research Council of Canada, 1200 Montreal Road, M-12, Ottawa, Ontario K1A 0R6, Canada.
ACS Omega. 2023 Apr 5;8(15):14219-14232. doi: 10.1021/acsomega.3c01127. eCollection 2023 Apr 18.
Single-walled carbon nanotubes (SWCNTs) are candidate matrices for loading metal nanoparticles (NPs) for sensor and catalytic applications owing to their high electron conductivity and mechanical strength, larger surface area, excellent chemical stability, and ease of surface modification. The performance of the formed NP/SWCNT composites is dependent on the NP size, the physical and chemical interactions between the components, and the charge transfer capabilities. Anchoring metal complexes onto the surface of SWCNTs through noncovalent interactions is a viable strategy for achieving high-level metal dispersion and high charge transfer capacities between metal NPs and SWCNTs. However, traditional metal complexes have small molecular sizes, and their noncovalent interactions with SWCNTs are limited to provide excellent sensing and catalytic capability with restricted efficiency and durability. Here, we selected poly(9,9-di--dodecylfluorenyl-2,7-diyl--2,2'-bipyridine-5,5') (PFBPy) to increase the noncovalent interactions between silver nanoparticles (AgNPs) and SWCNTs. A silver triflate (Ag-OTf) solution was added into a PFBPy-wrapped SWCNT solution to form Ag-PFBPy complexes on the nanotube surface, after which Ag was photoreduced to AgNPs to form a Ag-PFBPy/SWCNT composite in the solution. In various feeding molar ratios of Ag-OTf over the BPy unit (0.4-50), the size of the formed AgNPs may be well-controlled at sub-nm levels to provide them with an energy level comparable to that of the SWCNTs. Additionally, the 2,2'-bipyridine (BPy) unit of the polymer provided a coordinating interaction with Ag and the formed AgNPs as well. The 5,5'-linage of BPy with the fluorene unit in PFBPy ensured a straight main chain structure to retain strong π-π interactions with nanotubes before and after Ag chelation. All of these factors confirmed a tight contact between the formed AgNPs and SWCNTs, promoting the charge transfer between them and enhancing the sensing capabilities with a 5-fold increase in humidity sensing sensitivity.
单壁碳纳米管(SWCNTs)因其高电子导电性和机械强度、较大的表面积、优异的化学稳定性以及易于表面改性,而成为用于负载金属纳米颗粒(NPs)以用于传感器和催化应用的候选基体。所形成的NP/SWCNT复合材料的性能取决于NP的尺寸、各组分之间的物理和化学相互作用以及电荷转移能力。通过非共价相互作用将金属配合物锚定在SWCNTs表面是实现金属NP在SWCNTs之间高水平分散以及高电荷转移能力的可行策略。然而,传统金属配合物的分子尺寸较小,它们与SWCNTs的非共价相互作用有限,难以提供具有受限效率和耐久性的优异传感和催化能力。在此,我们选择聚(9,9-二-十二烷基芴基-2,7-二基-2,2'-联吡啶-5,5')(PFBPy)来增强银纳米颗粒(AgNPs)与SWCNTs之间的非共价相互作用。将三氟甲磺酸银(Ag-OTf)溶液加入到PFBPy包裹的SWCNT溶液中,在纳米管表面形成Ag-PFBPy配合物,之后将Ag光还原为AgNPs,在溶液中形成Ag-PFBPy/SWCNT复合材料。在Ag-OTf与联吡啶(BPy)单元的各种进料摩尔比(0.4-50)下,所形成的AgNPs的尺寸可以在亚纳米水平上得到很好的控制,使其具有与SWCNTs相当的能级。此外,聚合物的2,2'-联吡啶(BPy)单元也与Ag以及所形成的AgNPs提供了配位相互作用。BPy在PFBPy中与芴基单元的5,5'-连接确保了主链结构笔直,在Ag螯合前后都能与纳米管保持强烈的π-π相互作用。所有这些因素都证实了所形成的AgNPs与SWCNTs之间的紧密接触,促进了它们之间的电荷转移,并将湿度传感灵敏度提高了5倍,增强了传感能力。